Monitoring UV absorption signals of SiF2 and SiF, the thermal dissociation reactions of SiF4 and SiF2 were studied in shock waves. Rationalizing the experimental observations by standard unimolecular rate theory in combination with quantum-chemical calculations of the reaction potentials, rate constants for the thermal dissociation reactions of SiF4, SiF3, and SiF2 and their reverse recombination reactions were determined over broad temperature and pressure ranges. A comparison of fluorosilicon and fluorocarbon chemistry was finally made.